The principle of lithography technique is based on the unmixability of oil and water, and wherein oily material or printing ink are according to qualifications attached to the image domain, and water or fountain solution are then according to qualifications attached to non-image domain.When drenching through suitably prepd surperficial water and during stencil, water is intercepted and captured in background or non-image domain, the image domain is is then intercepted and captured printing ink and is repelled water.The printing ink of image domain is transferred to the material surface of preparing display image, for example surface of paper, cloth and so on subsequently.Usually, printing ink is transferred to earlier on a kind of intermediate materials that is called blanket, printing ink is transferred to the material surface of display image by it again.
A kind of common type of lithographic plate predecessor comprises the photosensitive coating that is applied in aluminium base support.Negative lithographic printing version predecessor has a kind of radiation-sensitive coating, and it hardens in the exposure area when exposing with image mode.After development, the non-exposed area of coating composition is removed, and the result stays image.On the other hand, positive working lithographic printing version predecessor comprises a kind of like this coating composition, and after being exposed to the illumination of suitable wavelength with image mode, its dissolubility in exposure region becomes greater than the non-exposed area in developer solution.This photoinduced poor solubility alienation is called ploto solubilization.Scribble the quinone diazide together with a large amount of commercially available positive Plate making printing version predecessor of phenolic resins according to the work of ploto solubilization principle to produce image.In both cases, the imaging district of galley itself is oil suction China ink or oleophylic, but not area of image or background are suction or hydrophilic.
In exposure process, produced difference between the visual and non-area of image, film on galley predecessor loam cake vacuumizes simultaneously to guarantee excellent contact therebetween.Then, galley predecessor is exposed to light source, and a part is made of ultra-violet radiation in the light source.Under the situation of using positive Plate making printing version predecessor, with the visual corresponding film district in the galley predecessor be opaque, therefore light is beaten less than in the galley predecessor, the district then is transparent with the corresponding film of non-area of image, therefore allow light to be transmitted on the coating, it just becomes more solvable, so be removed.
But the radiation-sensitive composition that the more new development in lithographic plate predecessor field provides the galley predecessor of preparation laser direct addressin to use.Digital imaging information can be used to the imaging to the galley predecessor, need not to utilize the imaging mother matrix such as the photograph transparency.
But positive plate-making laser addressed galley predecessor's example can be seen in United States Patent (USP) 4,708, and on November 24th, 925,1987 authorized.A kind of like this lithographic plate of this patent description predecessor, wherein the imaging layer comprises phenolic resins and radiosensitive salt.Described as this patent, phenolic resins and this salt interact and generate a kind of alkali insoluble group compound, and it reverts to alkali again after this salt generation light decomposes soluble.This galley predecessor can be used as positive Plate making printing version predecessor or negative Plate making printing version predecessor, still needs in exposure and between developing therebetween and adopts some additional processing step, can see BP 2,082 for details, 339.United States Patent (USP) 4,708,925 described galley predecessors are in itself to the ultra-violet radiation sensitivity, and in addition also to visible light and sensitive for infrared radiation.
Another example of laser addressed galley predecessor, it can be used as a kind of direct positive plate-making system and uses, and is seen in United States Patent (USP) 5,372, and on December 13rd, 907,1994 authorized, and United States Patent (USP) was authorized on February 13rd, 5,491,046,1996.These two patents are described the radiation-induced decomposition of a kind of latent Blang Si Taide acid (Bronsted acid), to improve the solubility of resinous substrates after the image mode exposure.With United States Patent (USP) 4,708, the 925 galley predecessors that describe are the same, and this class system can also be used as negative plate-making system in addition, and take some additional processing step this moment after exposure, before developing.In negative plate-making process, decomposition by-products is used to the cross-linking reaction between the catalytic resin subsequently so that the preceding image domain of developing is insoluble.At United States Patent (USP) 4,708, mention in 925, this class galley predecessor is owing to used above-mentioned acidic material, in itself to the ultra-violet radiation sensitivity.
The various prior art galley predecessor who can be used for direct imaging positive Plate making printing version predecessor described above lacks one or more desirable features.Neither one can not need appropriately to consider the lighting condition of working region in occasion processing widely among these galley predecessors that described.In order to make these galley predecessor available indefinitely, require to prevent the specific safety lighting condition of unexpected exposure.This class galley predecessor can only can use in the limited time limit under the white light condition of work, and specified period is decided according to the output spectrum of this white light source.If can use digital imaging hardware and galley predecessor in the environment of unrestricted, white light pressroom, so that workflow is rationalized, then will be desirable, and will be a shortcoming in this environment medium ultraviolet sensitiveness.In addition, white light operation can be traditional printing forefoot area--also having to be operated under the restricted emergency lighting condition at present in this zone--provide the working environment of improvement.
And, two kinds of galley predecessor systems are all to the additional restricted condition of its composition, this just gives every performance of optimizing forme, for lithographic plate performance parameter in extensive requirement, comprise developing solution dissolution, ink absorption, space of a whole page length, adhesive force etc., between provide the operation of optimization to cause all difficulties.
At United States Patent (USP) 4,708, in the 925 described systems, do not allow existence can make irradiation back phenolic resins that crosslinked various functional groups take place in the presence of salt, no matter it is for alkali soluble resin is carried out modification, still a kind of adding ingredient as composition adds, the reduction of back solubilization effect because this will cause exposing.
United States Patent (USP) 5,491, a basic demand of 046 described composition requires resole resin and phenolic novolac to exist simultaneously exactly, so that allow this system to use by negative plate-making mode.And this mode is the optimal way of this system, as first commercially produced product that its negative is made a plate patent example and is transformed by this proprietary technology, and the Performer product of Kodak, shown.This optimization to negative plate-making potential use has but limited the optimization to the positive plate-making mode that does not have this requirement.
Various hot solubilizing composition as the thermal imaging recording materials once was disclosed in BP 1 before this, 245, in 924, on September 15th, 1971 authorized, wherein write, but the dissolubility of any given area in given solvent can be exposed to highdensity visible light and/or infra-red radiation is improved this layer heating indirectly by the short time in the imaging layer, this kind light or radiation from the transmission or the reflection of the contacted plate-making original copy of recording materials background area.Described system is various, and operates and use different developing materials from water to the chlorinated organic solvent by many different mechanisms.The disclosed myriad combinations thing that adopts water-bearing media to develop comprises that those contain the composition of novolac resin class.This patent proposes, and contains this resinoid coated film and will show higher dissolubility after heating.Can contain endothermic compound in this based composition, for example carbon black or Milori Blue (C.I.PigmentBlue27).These materials also make image painted when using as recording medium simultaneously.
Yet, BP 1,245, dissolubility difference degree is but very little with comparing of commercially available positive working lithographic printing version precursor composition in 924 described each composition.The lithographic plate predecessor of standard can show excellent tolerance to strong developer solution, the good adaptability of the various changing factors during the user is used, and can be optimized, thereby high developer solution utilization rate is provided and can prints a lot of numbers.BP 1,245, the developer solution tolerance of the extreme difference that 924 compositions table reveals makes it be not suitable as commercial acceptable lithographic plate predecessor.
We find a kind of heat-sensitive composition that is suitable as the heat-sensitive positive-working Plate making printing version predecessor of hot mode imaging, and it does not have the shortcoming that top said prior art exists.
Why composition of the present invention is temperature-sensitive, is because composition is subjected to local heat, preferably by suitable radiation, thereby causes the moisture developing solution dissolution increase in exposure area.
Therefore, according to one aspect of the present invention, a kind of lipophile heat-sensitive composition is provided, it comprises a kind of polymeric material that dissolves in moisture developer solution, below be called " living polymer " and a kind ofly can reduce this polymeric material deliquescent compound in moisture developer solution, below be called " reversible insoluble compound " (reversible insolubiliser compound), it is characterized in that, the moisture developing solution dissolution of said composition improves because of being heated, and the moisture developing solution dissolution of said composition does not improve because of the incident of ultra-violet radiation.
According to another aspect of the present invention, a kind of positive working lithographic printing version predecessor is provided, it comprises the coating that is made of a kind of composition, said composition contains described living polymer and described reversible insoluble compound, this coating is coated on the support on possess hydrophilic property surface, it is characterized in that the moisture developing solution dissolution of said composition improves because of being heated, and the moisture developing solution dissolution of said composition does not improve because of the incident of ultra-violet radiation.
In order to improve the sensitivity of heat-sensitive composition of the present invention, it is useful adding additional composition therein, promptly adds a kind of compound that can absorb the radiation of incident and be translated into the absorption radiation of heat, below is called " radiation absorbing compound ".
Therefore, another aspect of the present invention is the lithographic plate predecessor, and wherein said coating is suitable for the preferential adsorption radiation suitably and described radiation is converted into heat.
And then, according to a preferred embodiment of the present invention, heat-sensitive positive-working lithographic printing version predecessor is provided, it is included in a kind of oleophylic heat-sensitive composition on the support with water-wetted surface, said composition comprises described living polymer, described reversible insoluble compound and described radiation absorbing compound, it is characterized in that the moisture developing solution dissolution of said composition improves because of being heated, and the moisture developing solution dissolution of said composition does not improve because of the incident of ultra-violet radiation.
In the further preferred embodiment of the present invention, a kind of heat-sensitive positive-working lithographic printing version predecessor is provided, wherein said coating comprises the extra play that is arranged under this oleophylic heat-sensitive composition, and wherein this extra play contains radiation absorbing compound.
In another further preferred embodiment of the present invention, a kind of heat-sensitive positive-working lithographic printing version predecessor is provided, it is included in a kind of oleophylic heat-sensitive composition on the support with water-wetted surface, said composition comprises described living polymer and also is the described reversible insoluble compound of described radiation absorbing compound simultaneously, it is characterized in that, the moisture developing solution dissolution of said composition improves because of being heated, and the moisture developing solution dissolution of said composition does not improve because of the incident of ultra-violet radiation.
In this manual, when the moisture developing solution dissolution of mentioning composition when us improved because of being heated, we were meant that it has improved significantly, have promptly improved one and have been the available quantity of lithography process.When the moisture developing solution dissolution of saying composition when us did not increase because of the incident of ultra-violet radiation, we were meant that its does not significantly increase, and does not promptly increase a quantity of having to adopt ultraviolet emergency lighting condition.Therefore, unconspicuous recruitment is admissible within the scope of the invention behind the ultra-violet radiation.
This galley is lithographic plate preferably, hereinafter will call it like this.
So, in all preferred embodiments of the present invention, obtaining positive working lithographic printing plates with the hot mode imaging and after handling.The moisture developing solution dissolution of its coating composition is to greatly reduce with respect to the dissolubility of living polymer itself.After being exposed to suitable radiation subsequently, the heat affected zone of said composition just becomes easier and has been dissolved in developing solution.Therefore, after with the image mode exposure, variation has taken place in dissolubility difference between unexposed composition and exposure composition.So at exposure region, composition is dissolved have been fallen, and exposes the water-wetted surface under the forme.
Clad plate of the present invention can by the short time be exposed to from the high strength transmission or the reflected radiation of the contacted plate-making original copy of recording materials background area, thereby thermal imaging indirectly.
Aspect another, preferably utilize a kind of calandria that this plate is heated with image mode in the present invention.For example, the reverse side of this plate, perhaps preferably, heat-sensitive composition can contact with hot contact pilotage.
Aspect another, this plate preferably directly exposes by laser, thereby with image mode coating is heated in the present invention.Most preferably, this laser instrument is launched the above radiation of 600 nanometers.
Although the applicant does not intend being subject to the explanation about its invention work theory, it is believed that between living polymer and reversible insoluble compound to have formed a kind of thermally labile complex.This complex it is believed that it is reversible formation, thus this complex can decompose by heating, thereby recover the moisture developing solution dissolution of said composition.It is believed that, be fit to polymeric material that the present invention uses contains rich electronics when not cooperating functional group, the suitable combination thing of moisture developing solution dissolution that can reduce this polymeric material is then for short of electricity.Do not think that the composition in the requirement said composition decomposes, do not think in any proof so far any example, any significant decomposition reaction to occur yet.
The example of the functional group of the described living polymer that suitable the present invention uses comprises: hydroxyl, carboxylic acid, amino, acid amides and maleimide amine functional group.Have diversified polymeric material to be fit to the present invention and use, its example comprises: phenolic resins; The copolymer of 4-oxybenzene ethene and for example 3-methyl-4-oxybenzene ethene or 4-methoxy styrene; (methyl) acrylic acid and for example cinnamic copolymer; Maleimide (maleiimide) and for example cinnamic copolymer; Hydroxyl or carboxy-functionalized cellulose; Maleic anhydride and for example cinnamic copolymer; The maleic anhydride polymer of partial hydrolysis.
Most preferred living polymer is a phenolic resins.The phenolic resins that the present invention is particularly useful is the condensation product that reacts to each other between phenols (for example cresols and p-t-butyl phenol), bisphenols (for example bisphenol-A) and the aldehydes (for example formaldehyde) that replaces from phenol, C-alkyl.According to the preparation route of condensation product, can generate varied aldehydes matter with different structure and characteristic.What the present invention was particularly useful is the mixture of novolac resin, resole resin (resole) and line style/resole resin.The example of suitable novolac resin has following general structure.
Found a large amount of water miscible compounds of suitable polymeric material that can reduce to can be used as this reversible insoluble compound.
A useful class is such class nitrogen-containing compound in the reversible insoluble compound, wherein at least one nitrogen-atoms or quaternised, be contained in the heterocycle, perhaps be quaternised being contained in again among the heterocycle.
The example that contains the useful compound of quaternized nitrogen-atoms is a triarylmethane dye, for example CrystalViolet (crystal violet) (CI alkaline purple 3) and Ethyl Violet (ethyl violet) and tetraalkyl ammonium compound, for example Cetrimide.
More preferably, this reversible insoluble compound is a nitrogen-containing heterocycle compound.
The example of suitable nitrogen-containing heterocycle compound is quinoline and triazole type (triazols), for example 1,2, the 4-triazole (1,2,4-triazol).
Most preferred reversible insoluble compound is quaternised heterocyclic compound.
The example of suitable quaternized heterocyclic compound is an imidazolinium compounds, for example MonazolineC, Monazoline O, Monazoline CY and Monazoline T, all these are made by Mona industrial group, quinoline compound, for example iodate 1-ethyl-2-methylquinoline and iodate 1-ethyl-4-methylquinoline, and benzothiazole (benzothiazolium) compound, iodate 3-ethyl-2-methylbenzothiazole for example, and pyridine compounds, for example cetylpyridinium bromide, two bromoethyl viologen and tetrafluoro boric acid fluorinated pyridine.
Usefully, this quinoline or benzothiazole compound are the cation cyanine dyes, for example DyeA (dyestuff A), Quinoldine Blue and iodate 3-ethyl-2-[3-(3-ethyl-2 (3H)-benzothiazole subunit)-2-methyl isophthalic acid-acrylic] benzothiazole,
The another kind of carbonyl functional group's compound that usefully contains in the reversible insoluble compound.
The suitable example that contains carbonyl functional group's compound is α-naphthoflavene, β-naphthoflavene, 2,3-diphenyl-1-indone, flavones, flavanones, xanthene ketone, benzophenone, N-(4-brombutyl) phthalimide and phenanthrenequione.
Reversible insoluble compound can be the following compound of general formula:
Q
1-S(O)
n-Q
2
Q wherein
1Phenyl or alkyl that representative randomly replaces, n represents 0,1 or 2, Q
2Represent halogen atom or alkoxyl.Preferably, Q
1Represent C
1-4Alkyl phenyl, for example tolyl, or C
1-4Alkyl.N preferably represent 1 or, especially 2.Q
2Preferably represent chlorine atom or C
1-4Alkoxyl, especially ethyoxyl.
Another kind of useful reversible insoluble compound is acridine orange base (a CI solvent orange 15).
Other useful reversible insoluble compounds are ferrocene (ferrocenium) compound, for example hexafluorophosphoric acid ferrocene.
Except with reversible insoluble compound according to the interactional reactive compound of the mode of this paper defined, said composition also can contain and not participate in interactional polymeric material like this.In the composition of this blend that contains polymeric material, should be noted that the content (by weight) of this living polymer can be lower than additional polymeric material.Suitable is, the content of living polymer in the gross weight of the polymeric material that exists in the composition, is 10% at least, preferably at least 25%, more preferably at least 50%.Yet most preferably, except this living polymer, there is not any interactional polymeric material not like this.
The major part of said composition preferably is made of polymeric material, it comprise living polymer and, if any, additional interactional polymeric material not like this.Preferably, the less important part of said composition is made of reversible insoluble compound.
The major part of this paper defined is advisable to be equivalent to 50% of composition total weight at least, and preferably at least 65%, most preferably at least 80%.
The less important part of this paper defined is advisable below 50% with composition total weight, and preferred maximum 20%, most preferably maximum 15%.
Suitable is, reversible insoluble compound accounts at least 1% of composition total weight, preferably at least 2%, preferably maximum 25%, more preferably maximum 15%.
Therefore, the preferred weight range of reversible insoluble compound can be expressed as: 2~15% of composition total weight.
May exist more than one and the interactional polymeric material of described compound.When this paper mentions the ratio of this type of material, be the total content that refers to them.Equally, may exist more than one interactional polymeric materials not like this.When this paper mentions the ratio of this type of material, be the total content that refers to them.Equally, may exist more than one reversible insoluble compounds.When this paper mentions the ratio of this type of material, be the total content that refers to them.
The composition of moisture developer solution is decided according to the character of polymeric material.The composition commonly used of moisture lithographic plate developer solution is the salt of surfactant, chelating agent such as ethylenediamine tetra-acetic acid, organic solvent such as phenmethylol, and alkaline components such as inorganic silicate, organosilicate, hydroxide or bicarbonate.
Preferably, when polymeric material was phenolic resins, this moisture developer solution was the alkaline-based developer that contains inorganic silicate, perhaps contained the alkaline-based developer of organic silicate.
6 simple experiments are arranged, and test 1~6 can be used to determine that certain contains living polymer and reversible insoluble compound compositions and certain suitable moisture developer solution and whether is suitable for the present invention.
Test 1
The composition that contains living polymer that does not contain reversible insoluble compound is applied on the hydrophily support and drying.Subsequently, give this oil surface China ink.If what obtain when being coated with to one deck is uniform ink coating, then said composition is an oleophylic.
Test 2
The hydrophily support that has been coated with the composition that contains living polymer that does not contain reversible insoluble compound is handled reasonable time in the suitable moisture developer solution of room temperature, this time can be determined by the examination difference, and typically be 30~60 seconds, cleaning then, the dry printing ink of also going up.If can not get ink pellet surface, then said composition has been dissolved in developer solution and has suffered.
Test 3
Containing living polymer and reversible insoluble compound compositions is applied on the hydrophily support and drying.Subsequently, give this oil surface China ink.If what obtain when being coated with to one deck is uniform ink coating, then said composition is an oleophylic.
Test 4
Be coated with the hydrophily support that contains living polymer and reversible insoluble compound compositions and in the suitable moisture developer solution of room temperature, handled reasonable time, this time can be determined by the examination difference, and typically be 30~60 seconds, cleaning then, the dry printing ink of also going up.If obtain uniform ink coating, then said composition is insoluble to this developer solution basically.
Test 5
Be coated with the hydrophily support that contains living polymer and reversible insoluble compound compositions and in baking oven, heated, made said composition reach suitable temperature and keep reasonable time.Place it in then in the suitable moisture developer solution of room temperature and handle reasonable time.
This surface subsequent drying is also gone up printing ink.If can not get ink pellet surface, then the composition of this heating has been dissolved in developer solution and has suffered.
Temperature and time should be determined according to composition selected composition and ratio thereof.Can test to determine appropriate condition by simple examination difference.If can not find the condition that satisfies test standard from these tests, then conclusion must be that said composition can't pass this test.
For typical composition preferably, contain living polymer and reversible insoluble compound compositions heats in baking oven, allow composition reach 50 ℃~160 ℃ temperature and kept for 5~20 seconds.Subsequently, sample is handled reasonable time in the suitable moisture developer solution of room temperature, and this time can be definite by the test of examination difference, and typically between 30~120 seconds.
Most preferably, contain living polymer and reversible insoluble compound compositions heats in baking oven, allow composition reach 50 ℃~120 ℃ temperature and kept for 10~15 seconds.Subsequently, said composition handled for 30~90 seconds in the suitable moisture developer solution of room temperature.
Test 6
Be coated with the hydrophily support that contains living polymer and the reversible insoluble compound compositions one section reasonable time that exposes under ultraviolet light, this time can determine by the test of examination difference, and typically is for 30 seconds.Subsequently, sample is handled reasonable time in the suitable moisture developer solution of room temperature, and this time can be definite by the test of examination difference, and typically be for 30~60 seconds.Then, its surface is through super-dry and upward black.If show printing ink on the coating, then ultra-violet radiation does not take place and induces solubilising in said composition, thereby said composition is enough to tolerate normal operating illumination condition.
If composition has passed through 6 all tests, then it is suitable for the present invention.
There are a large amount of compounds or its combination to can be used as radiation absorbing compound in the preferred embodiments of the invention.
In preferred embodiments, this radiation absorbing compound can absorb infra-red radiation.But, also can use to absorb other wavelength radiation other materials of (not comprising ultraviolet wavelength), for example from the radiation of 488 nanometers in argon laser source, radiation this moment also is converted into heat.
Radiation absorbing compound is useful with carbon, for example carbon black or graphite.It can be commercially available pigment, for example the Heliogen Green of BASF AG's supply, perhaps the Nigrosine Base NG1 of NH Laboratories company supply, perhaps the Milori Blue (C.I.Pigment Blue27) of Aldrich company supply.
In a preferred method of the invention, clad plate directly exposes with image mode with laser instrument.Most preferred laser instrument sends the above radiation of 600 nanometers, absorbs the then available infrared absorbing dye of compound of this radiation.
Preferably, this infrared absorbing compounds is that the laser output wavelength place that those its absorption spectras prepare to use in the methods of the invention is significant compound.Useful can be such as phthalocyanine color organic pigment or dyestuff.Perhaps, it can be class dyestuff or pigment such as square aryl (aquarylium), merocyanine, cyanine, indolizine, pyrans or metal ithioline.
The example of this compounds is:
And dyestuff B
And dyestuff C, promptly by the KF654 B PINA of Riedel de Haen UK company (Middlesex, Britain) supply, its structure it is believed that into:
Suitable radiation absorbing compound accounts at least 1% of composition total weight, and preferably at least 2%, preferably maximum 25%, more preferably maximum 15%.Therefore the preferred weight range of radiation absorbing compound can be expressed as 2~15% of composition total weight.The radiation absorbing compound that more than one can be arranged equally.During every ratio of mentioning this compounds, all refer to their total content.
In a preferred embodiment of the invention, can use a kind of extra play that comprises radiation absorbing compound.This sandwich construction can provide the approach that reaches high sensitivity, because can use the absorbent of larger amt and the unlikely function that has influence on the imaging layer.In principle, can in the wave-length coverage of hope, have enough the radiation-absorbing material of strong absorbability in conjunction with entering or making uniform coating with any.Dyestuff, metal and pigment can be made (comprising metal oxide) form of vapor deposition layer and use, and the using method of its forming technique and this type of film is known technically, for example can be referring to European patent 0,652,483.Preferred for this invention this kind of composition is that those are hydrophilic, make the uniform coating form or through processing the composition that hydrophilic surface can be provided, for example add a hydrophilic layer.
The moisture developing solution dissolution that can reduce polymeric material is again simultaneously a radiation absorbing compound and be suitable in one embodiment of the invention compound, and preferably cyanine dye most preferably is that absworption peak is positioned at the above quinoline cyanine dye of 600 nanometers.
The example of this compounds is:
Bromination 2-[3-chloro-5-(1-ethyl-2 (1H)-quinoline subunit)-1,3-pentadiene base]-1-ethyl quinoline
Iodate 1-ethyl-2-[5-(1-ethyl-2 (1H)-quinoline subunit)-1,3-pentadiene base] quinoline
Iodate 4-[3-chloro-5-(1-ethyl-4 (1H)-quinoline subunit)-1,3-pentadiene base]-1-ethyl quinoline
Dyestuff D, iodate 1-ethyl-4-[5-(1-ethyl-4 (1H)-quinoline subunit)-1,3-pentadiene base] quinoline
Suitable is, is again simultaneously that the reversible insoluble compound of radiation absorbing compound accounts at least 1% of composition total weight, preferably at least 2%, preferably maximum 25%, more preferably maximum 15%.Therefore, simultaneously be again that reversible insoluble compound shared preferred weight range in composition of radiation absorbing compound can be expressed as 2~15% of composition total weight.
The version base aluminium sheet preferably that can be used as support, its is through being known common anode granulation and the anode post processing of lithographic techniques, thereby radiation-sensitive composition can be coated with in its surface and make this carrier surface play the function of printing background.
Spendable another kind of version sill is photographic industry sheet of plastics material base commonly used or treated scraps of paper base in the inventive method.Useful especially sheet of plastics material base is a PET, and its surface becomes water-wetted surface through gluing.Also have, also can use a kind of so-called resinous coat paper through Corona discharge Treatment.
The example that can be used for the lasing light emitter in the inventive method comprises that transmitting boundary is at the semiconductor diode laser of 600 nanometers to 1100 nanometers.An example is a Nd YAG laser instrument, and transmitting boundary is in 1064 nanometers, but any laser instrument (its radiant energy is absorbed by said composition) with enough imaging abilities all can use.
Composition of the present invention as in many lithographic printing-plate compositions, also can contain other compositions, for example stabilization additives, inertia colouring agent, additional inert polymer adhesive.
Preferably, heat-sensitive composition of the present invention does not contain the ultraviolet sensitivity composition.But can contain because of other compositions for example the existence on inertia UV absorption dyestuff or UV absorption top layer not by the ultraviolet sensitivity composition of UV-activated.
Any feature of the present invention or any aspect described herein can combine with any feature of any other aspect of any invention or embodiment described herein.
Following embodiment more specifically for example understands the so far described various aspects of the present invention of this paper.
Following products will be mentioned hereinafter:
Resin A: LB6564-phenol/cresols novolac resin, Bakelite company sells.
Resin B: R17620-phenol/formaldehyde resole resin, B.P. chemical company (Sully, Wales) produces.
Resin C:SMD995-alkylphenol/formaldehyde resole resin, SchnectadyMidland company (Wolverhampton, Britain) produces.
Resin D:Maruka Lyncur M (S-2)-polyhydroxystyrene resin, Maruzen petrochemistry company (Tokyo, Japan) produces.
Resin E:Ronacoat 300-main component is the polymer of dimethyl maleimide, and Rohner company (Pratteln, Switzerland) produces.
Resin F:Gantrez An119-methyl vinyl ether-CO-maleic anhydride copolymers, Gaf chemical company (Guildford, Britain) produces.
Resin G:SMA 2625P-SMA styrene maleic anhydride half ester, Elf Atochem UK company (Newbury, Britain) produces.
Resin H: cellulose ethanoate propionic ester (molecular weight 75,000 contains acetic acid esters 2.5% and propionic ester 45%~49%), Eastman fine chemistry company (Rochester, the U.S.) produces.
The light exposure test method
Treat that the sheet base that scribbles coating of imaging is cut into the disk of 105 mm dias, place one can 100~2500 rev/mins on the disk of constant rotational speed rotation., individual transfer table is arranged at rotating circular disk on one side, adorning laser beam sources on it, in order to laser beam is adjusted to the position perpendicular to the sheet base that scribbles coating, meanwhile, transfer table can radially move laser beam with linear mode with respect to rotary disk.
The laser instrument that uses is 200 milliwatt laser diodes of folk prescription formula 830 nano wave lengths, focuses on 10 microns resolution ratio.The power supply of laser instrument is stable, constant-current power supply.
The image of exposure is a spiral form, so the image of spiral center represents slow laser scanning speed and long time for exposure, and the outward flange of spiral is then represented fast scan speed and short exposure time.The imaging energy is to calculate out from the visual measuring diameter value that forms.
The least energy that this exposure system can send is 150 millijoule/square centimeters in the time of 2500 rev/mins.
Comparative Examples C1~C5 and example 1~9
The coating formula of all examples all is prepared to the solution form in 1-methoxyl group propan-2-ol, what make an exception is: example 4,5 and 8, being prepared in volume ratio is solution among 1-methoxyl group propan-2-ol/DMF (dimethyl formamide) of 40: 60, and example 7 is the solution among 1-methoxyl group propan-2-ol/DMF (dimethyl formamide) of 35: 65 for volume ratio.The sheet base that uses is 0.3 millimeter aluminium flake, and it has passed through electrochondriaization and anodization, and carries out post processing with the inorganic phosphate saline solution.With twining rod wiry coating solution is applied on the sheet base.Select this solution concentration, so that following dry film composition is provided, it is 1.3 grams through every square metre of coating weight of drying after 3 minutes in 100 ℃ baking oven.
| Comparative Examples |
????C1 | ????C2 | ????C3 | ????C4 | ????C5 |
Composition | Weight portion |
Resin A | ???100 | ???95.7 | ????90 | ????90 | ????90 |
Dyestuff B | | ???4.25 | ????4 | ????4 | ????4 |
Benzoic acid | | | ????6 | | |
P-nitrophenol | | | | ????6 | |
3 ', 3 ", 5 ', 5 "-tetrabromo phenyl phthalein | | | | | ????6 |
| Example |
??1 | ??2 | ??3 | ???4 | ???5 | ???6 | ???7 | ???8 | ???9 |
Composition | Weight portion |
Resin A | ??86 | ??90 | ??90 | ??90 | ??90 | ??90 | ??90 | ??90 | ??90 |
Dyestuff B | ??4 | ??4 | ??4 | ??4 | ??4 | ??4 | ??4 | ??4 | ??4 |
Dyestuff A | ??10 | | | | | | | | |
Bromination 1-ethyl-4-methylquinoline | | ??6 | | | | | | | |
????Monazoline?C | | | ????6 | | | | | | |
Benzothiazole A | | | | ????6 | | | | | |
Benzothiazole B | | | | | ??6 | | | | |
Cetylpyridinium bromide | | | | | | ????6 | | | |
Dibrominated ethyl viologen | | | | | | | ??6 | | |
????Cetrimide | | | | | | | | ??6 | |
Crystal violet | | | | | | | | | ??6 |
Benzothiazole A is bromination 3-ethyl-2-[3-ethyl-2 (3H)-benzothiazole subunit)-2-methyl isophthalic acid-acrylic] benzothiazole.
Benzothiazole B is iodate 3-ethyl-2-methylbenzothiazole.
The sample board forme was soaked for 30 seconds in moisture developer solution, to its development property test.What use is following suitable moisture developer solution.
Developer solution A:14% five silicate hydrate sodium water solutions.
Developer solution B:7% five silicate hydrate sodium water solutions.
Following table is listed the result of the simple development test that each composition is carried out.
| Developer solution B |
Comparative Examples |
????1~5 | Coating comes off fully |
Example | |
????1~9 | There is not obvious coating shedding |
The composition of describing in the Comparative Examples can not demonstrate the ability of anti-developer solution effect.The compositions display of describing in the example 1~9 goes out following effect: the compound of describing in the application of the invention, the polymer dissolubility in developer solution has reduced.
Subsequently, other sample formes carry out the image exposure by the laser instrument of above-described 830 nanometers.Then, the exposure disk is received in the processing of soaking for 30 seconds in the suitable as mentioned above developing aqueous solution.Measure the sensitivity of forme.
The result is provided in the table below.
| Developer solution A | Developer solution B |
Comparative Examples |
????1 | Do not stay coating |
????2 | Do not stay coating |
????3 | Do not stay coating |
????4 | Do not stay coating |
????5 | Do not stay coating |
Example | |
????1 | | ≤ 150 millijoule/square centimeters |
????2 | ≤ 150 millijoule/square centimeters | |
????3 | ≤ 150 millijoule/square centimeters | |
????4 | ≤ 150 millijoule/square centimeters | |
????5 | ≤ 150 millijoule/square centimeters | |
????6 | ≤ 150 millijoule/square centimeters | |
????7 | | ≤ 150 millijoule/square centimeters |
????8 | | ≤ 150 millijoule/square centimeters |
????9 | ≤ 150 millijoule/square centimeters | |
The one bar printing version of making according to example 1 is also at a kind of commercially available imaging setter--Trendsetter, supplier Creo Products company, and Vancouver, Canada--go up imaging.This plate is placed on and has printed at least 10,000 good printed matter on the offset press.
Example 10
Prepared a kind of solution that contains 8.15 gram 1-methoxyl group propan-2-ols, 2.40 gram 40%w/w Resin A solution, 0.12 gram dyestuff A and 0.24 gram 50% (w/w) carbon black aqueous dispersion in 1-methoxyl group propan-2-ol, and it has been coated with like that according to example 1~9.
| Example 10 |
Composition | Weight portion |
Resin A | ????80 |
Dyestuff A | ????10 |
Carbon black | ????10 |
Laser diode with 200 milliwatts, wavelength 830 nanometers on the image device that the forme that obtains is described in the above carries out the image exposure.Then, this forme developed for 30 seconds with developer solution B.Producing suitably, the required imaging energy density of image is≤150 millijoule/square centimeters.
The one bar printing version of making according to example 10 is also at a kind of commercially available imaging setter--Trendsetter, supplier Creo Products company, and Vancouver, Canada--go up imaging.This forme is placed on and has printed at least 10,000 good printed matter on the offset press.
Example 11
As example 4 is described the contained preparation of compositions of following table the forme predecessor.
| Example 11 |
Composition | Weight portion |
Resin A | ????90 |
Dyestuff D | ????10 |
Laser diode with 200 milliwatts, wavelength 830 nanometers on the image device that the forme that obtains is described in the above carries out imaging.Then, this forme developed for 30 seconds with developer solution B.Producing suitably, the required imaging energy density of image is≤150 millijoule/square centimeters.
The one bar printing version of making according to example 11 is also at a kind of commercially available imaging setter--Teandsetter, supplier Creo Products company, and Vancouver, Canada--go up imaging.This forme is placed on and has printed at least 10,000 good printed matter on the offset press.
Example 12~18
The coating formula that as previously described, has prepared the solution form in 1-methoxyl group propan-2-ol, exception be: it is solution among 1-methoxyl group propan-2-ol/DMF (dimethyl formamide) of 80: 20 that example 16 is prepared in volume ratio.
Each batching is coated with like that according to example 1~9, obtains the dry film composition contained as following table.
| Example |
????12 | ????13 | ????14 | ????15 | ????16 | ????17 | ????18 |
Composition | Weight portion |
Crystal violet | ????6 | ????6 | ????6 | ????6 | ????6 | ????6 | ????6 |
Dyestuff C | ????4 | ????4 | ????4 | ????4 | ????4 | ????4 | ????4 |
Resin A | | ????45 | | | | | |
Resin B | ????90 | | | | | | |
Resin C | | ????45 | | | | | |
Resin D | | | ????90 | | | | |
Resin E | | | | ????90 | | | |
Resin F | | | | | ????90 | | |
Resin G | | | | | | ????90 | |
Resin H | | | | | | | ????90 |
Subsequently, the sample forme is carried out to 830 above-mentioned nanometer laser apparatuses and resembles.And then the disk of exposure soaks reasonable time in suitable moisture developer solution handles, and method is with reference to above and hereinafter.Measure the sensitivity of forme then.The result is provided in the table below.
Developer solution C:15% betanaphthyl ethoxylate, 5% phenmethylol, 2% nitrilotriacetic acid trisodium salt, 78% water.
Developer solution D:3% betanaphthyl ethoxylate, 1% phenmethylol, 2% nitrilotriacetic acid trisodium salt, 94% water.
Developer solution E:1.5% betanaphthyl ethoxylate, 0.5% phenmethylol, 1% nitrilotriacetic acid trisodium salt, 97% water.
| Developer solution | Time/second | Sensitivity |
Example | |
????12 | ????B | ????90 | 248 millijoule/square centimeters |
????13 | ????A | ????90 | 277 millijoule/square centimeters |
????14 | ????C | ????45 | 277 millijoule/square centimeters |
????15 | ????D | ????5 | 253 millijoule/square centimeters |
????16 | ????E | ????60 | 461 millijoule/square centimeters |
????17 | ????D | ????90 | 300 millijoule/square centimeters |
????18 | ????A | ????120 | 700 millijoule/square centimeters |
Example 19~30
The coating formula that as previously described, has prepared the solution form in 1-methoxyl group propan-2-ol, exception be: it is solution among 1-methoxyl group propan-2-ol/DMF (dimethyl formamide) of 50: 50 that example 26 is prepared in volume ratio.
Each batching is coated with like that according to example 1~9, obtains the dry film composition contained as following table.
| Example |
| ??19 | ??20 | ??21 | ??22 | ??23 | ??24 | ??25 | ??26 | ??27 | ??28 | ??29 | ??30 |
Composition | Weight portion |
Dyestuff B | ??4 | ??4 | ??4 | ??4 | ??4 | ??4 | ??4 | ??4 | | | | |
Dyestuff C | | | | | | | | | ??4 | ??4 | ??4 | ??4 |
Resin A | ??90 | ??90 | ??90 | ??90 | ??90 | ??90 | ??90 | ??90 | ??90 | ??90 | ??90 | ??90 |
α-naphthoflavene | ??6 | | | | | | | | | | | |
β-naphthoflavene | | ??6 | | | | | | | | | | |
Flavones | | | ??6 | | | | | | | | | |
Xanthene ketone | | | | ??6 | | | | | | | | |
Flavanones | | | | | ??6 | | | | | | | |
Benzophenone | | | | | | ??6 | | | | | | |
2,3-diphenyl-1-indone | | | | | | | ??6 | | | | | |
N-(4-brombutyl) phthalimide | | | | | | | | ??6 | | | | |
Phenanthrenequione | | | | | | | | | ??6 | | | |
Acridine orange base (CI solvent orange 15) | | | | | | | | | | ??6 | | |
Paratoluensulfonyl chloride | | | | | | | | | | | ??6 | |
Ethyl p-methyl benzenesulfonic acid ester | | | | | | | | | | | | ??6 |
Subsequently, the sample forme is carried out to 830 above-mentioned nanometer laser apparatuses and resembles.And then the disk of exposure soaks reasonable time in suitable moisture developer solution handles.Measure the sensitivity of forme then.The result is provided in the table below.
| Developer solution | Time/second | Sensitivity |
Example | |
????19 | ????A | ????30 | ≤ 150 millijoule/square centimeters |
????20 | ????A | ????30 | ≤ 150 millijoule/square centimeters |
????21 | ????A | ????30 | 290 millijoule/square centimeters |
????22 | ????A | ????30 | ≤ 150 millijoule/square centimeters |
????23 | ????A | ????30 | ≤ 150 millijoule/square centimeters |
????24 | ????B | ????30 | 220 millijoule/square centimeters |
????25 | ????B | ????30 | ≤ 150 millijoule/square centimeters |
????26 | ????B | ????15 | ≤ 150 millijoule/square centimeters |
????27 | ????B | ????60 | 250 millijoule/square centimeters |
????28 | ????A | ????90 | 250 millijoule/square centimeters |
????29 | ????B | ????10 | 400 millijoule/square centimeters |
????30 | ????B | ????60 | 250 millijoule/square centimeters |
Example 31
The coating formula that as previously described, has prepared the solution form in 1-methoxyl group propan-2-ol.Batching is coated with like that according to example 1~9, obtains the dry film composition contained as following table.
| Example 31 |
Composition | Weight portion |
Resin A | ????90 |
Dyestuff C | ????4 |
Crystal violet | ????6 |
The sample forme has carried out heat treatment, and thermal source is Weller Soldering Iron (soldering iron) EC 2100M, and temperature is 311 ℃.The speed that soldering iron moves on the space of a whole page is provided in the table below.Subsequently, the sample forme of exposure soaks in developer solution A and handles for 60 seconds.The result is provided in the table below.
Soldering iron is the movement velocity cel on the space of a whole page | Heating surface | Simple development result of the test |
?????????1 | The coat side of version | The heat affected zone coating all comes off |
?????????10 | The coat side of version | The heat affected zone coating all comes off |
?????????20 | The coat side of version | The heat affected zone coating all comes off |
?????????50 | The coat side of version | The heat affected zone coating all comes off |
?????????1 | The back side of version is promptly directly on aluminum support | The heat affected zone coating all comes off |
?????????10 | The back side of version is promptly directly on aluminum support | The heat affected zone coating all comes off |
In this manual, we say the suffered UV-irradiation that is everywhere.Those skilled in the art will know that the typical wave-length coverage of this ultraviolet light.But, point out that the typical wave-length coverage of ultraviolet light is 190 nanometers~400 nanometers for fear of misunderstanding.
The institute of disclosed in this manual all features (comprising appended any claim, summary and accompanying drawing) and/or disclosed any method or technology in steps, all can any compound mode combine, unless some is mutually exclusive at least for above-mentioned feature in these combinations and/or step.
Disclosed each feature in this explanation (comprising appended any claim, summary and accompanying drawing) all available service replaces in alternative features identical, of equal value or similar purpose, unless expressly point out in addition.Therefore, remove in addition and expressly point out, disclosed each feature all only is an example that belongs to series together that is made of all equivalences or similar characteristics.
The invention is not restricted to the details of above-mentioned embodiment.The present invention extends to the feature combination of any one character of innovation in disclosed all features in this specification (comprising appended any claim, summary and accompanying drawing) or any innovation, perhaps in this explanation disclosed any method or technology any one innovative step in steps or the step of any innovation make up.